Cationic triazatrimethine dyestuffs

ABSTRACT

The new cationic triazatrimethine dyestuffs of the formula    &lt;IMAGE&gt;  (I)  wherein the substituents B, Z, R2 and An(-) have the meaning given in the description, are suitable for dyeing and printing naturally occurring and synthetic materials.

The present invention relates to new cationic triazatrimethinedyestuffs, processes for their preparation and their use for dyeing andprinting naturally occurring and synthetic materials, in particularfibres of polyacrylonitrile and acid-modified polyesters and polyamides.

The new triazatrimethine dyestuffs correspond to the general formula (I)##STR2## wherein Z represents a radical of the formula ##STR3## whereinR³ represents hydrogen or an alkyl, alkenyl or aralkyl radical and

X represents the remaining members of a five-membered, optionallysubstituted and optionally fused partly unsaturated heterocyclic ringwhich contains one to three hereto atoms selected from the groupconsisting of oxygen, sulphur and nitrogen,

B represents alkylmercapto, arylmercapto or a radical of the formula##STR4## wherein R denotes hydrogen or an alkyl, alkenyl, acyl,cycloalkyl, aryl, aralkyl, amino, alkylamino, dialkylamino, arylamino,aralkylamino or heterocyclic radical and

R¹ denotes hydrogen or an alkyl, alkenyl or aralkyl radical, or

R and R¹ together with the nitrogen atom to which they are attached forma heterocyclic ring,

R₂ represents hydrogen or an alkyl, alkenyl, alkinyl or aralkyl radicaland

An.sup.(-) represents an anion,

and wherein the cyclic and acyclic radicals can contain non-ionicsubstituents and/or a carboxyl group.

Non-ionic substituents in the context of the present invention are thenon-dissociating substituents customary in dyestuff chemistry, such as,for example, cyano, hydroxyl, halogen, such as fluorine, chlorine orbromine, nitro, alkyl, mono- and dialkylamino, phenyl, alkoxy, acyloxy,alkoxycarbonyl and alkoxycarbonyloxy, alkyl and alkoxy preferablycontaining 1 to 4 C atoms and acyl representing, in particular, C₁ -C₄-alkylcarbonyl.

Alkyl radicals in the context of this invention, including those incomposite terms, such as alkylamino, are, for example, those having 1 to8, in particular 1 to 4, C atoms.

Substituents of the alkyl radicals R¹, R² and R³ are, for example,halogen, hydroxyl, C₁ -C₄ -alkoxy, phenyloxy, benzyloxy, C₁ -C₄-alkoxycarbonyl, carboxyl, amidocarbonyl or cyano, and halogenpreferably represents fluorine, chlorine and bromine. Alkenyl andalkinyl radicals are understood as meaning, in particular, those having2 to 5 C atoms.

Cycloalkyl represents, for example, cyclopentyl or cyclohexyl which isoptionally substituted by C₁ -C₄ -alkyl. Suitable acyl radicals are, forexample, C₁ -C₃ -alkylcarbonyl, benzoyl which is optionally substitutedby halogen or C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl, mono- and di-C₁ -C₄-alkylaminocarbonyl, benzylaminocarbonyl, C₁ -C₄ -alkylsulphonyl,phenylsulphonyl or di-C₁ -C₄ -alkylaminosulphonyl.

Aryl is understood as meaning, in general, phenyl or naphthyl, andaralkyl is understood as meaning benzyl and β-phenyl-C₂ -C₄ -alkyl. Thephenyl radicals can be substituted by, for example, 1 to 3 non-ionicradicals, such as halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ `C₄-alkoxycarbonyl, carboxyl, amidocarbonyl, cyano, nitro, amidosulphonyl,C₁ -C₃ -alkylcarbonylamino, benzoylamino, hetaryl or arylazo. Hetaryl isunderstood here as meaning, for example, benzothiazolyl which isoptionally substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

The radicals R and R¹, together with the nitrogen atom to which they arebonded, can preferably form a 5- or 6-membered ring, such aspyrrolidine, piperidine, morpholine, piperazine or N-methyl- orN-hydroxyethylpiperazine.

Possible anionic radicals are the organic and inorganic anions customaryfor cationic dyestuffs.

Colourless anions are preferred. The anion is in general determined bythe preparation process and any purification carried out on the crudedyestuff. The dyestuffs are in general present in the form of halides(in particular in the form of chlorides or bromides) or in the form ofmethosulphates, ethosulphates, sulphates or benzene- ortoluenesulphonates, or in the form of acetates. The anions can bereplaced by other anions in a known manner.

Preferred triazatrimethine dyestuffs of the formula (I) are thosewherein

Z represents a radical of the formula ##STR5## wherein R³ representshydrogen, C₁ -C₈ -alkyl, which is optionally substituted by hydroxyl,halogen, cyano, C₁ -C₄ -alkoxy, carboxyl, C₁ -C₄ -(di)-alkylamino, C₁-C₄ -alkoxycarbonyl or C₁ -C₄ -alkylsulphonyl, or represents C₂ -C₄-alkenyl, or represents phenyl-C₁ -C₂ -alkyl, which is optionallysubstituted by halogen, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy and

X represents the remaining members of a thiazoline, isothiazoline,benzothiazoline, 1,2,4-triazoline, 1,3,4-thiadiazoline, oxazoline,benzoxazoline, imidazoline, benzimidazoline, pyrazoline orbenzopyrazoline ring, which is in each case optionally mono- ordisubstituted by identical or different C₁ -C₈ -alkyl, which isoptionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy,carboxyl, C₁ -C₄ -(di)alkylamino, C₁ -C₄ -alkoxycarbonyl or C₁ -C₄-alkylsulphonyl, or represents C₂ -C₄ -alkenyl, or represents phenyl-C₁-C₂ -alkyl, which is optionally substituted by halogen, cyano, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy,

B represents a radical of the formula ##STR6## wherein R representshydrogen, a C₁ -C₈ -alkyl radical which is optionally substituted byhydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl, aminocarbonyl or C₁-C₄ -alkoxycarbonyl, a C₂ -C₄ -alkenyl radical, a cyclohexyl radicalwhich is optionally substituted by C₁ -C₄ -alkyl, a phenyl, benzyl orphenylethyl radical which is optionally substituted by halogen, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy, a C₁ -C₄ -alkyloxycarbonyl, mono- or di-C₁ -C₄-alkylaminocarbonyl, aminocarbonyl, mono- or di-C₁ -C₄-alkylaminosulphonyl, amino, C₁ -C₄ -alkylamino or C₁ -C₄ -dialkylaminoradical, or represents a phenylamino or benzylamino radical which ineach case is optionally substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxyand

R¹ represents hydrogen, a C₁ -C₈ -alkyl radical which is optionallysubstituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl,aminocarbonyl or C₁ -C₄ -alkoxycarbonyl, a C₂ -C₄ -alkenyl radical orrepresents a phenyl, benzyl or phenylethyl radical which in each case isoptionally substituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, and

R² represents hydrogen, a C₁ -C₈ -alkyl radical which is optionallysubstituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl,aminocarbonyl or C₁ -C₄ -alkoxycarbonyl, a C₂ -C₄ -alkenyl radical orrepresents benzyl or phenylethyl radical which in each case isoptionally substituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

Particularly preferred dyestuffs of the formula (I) are those wherein

Z represents a radical of the formula ##STR7## wherein Y represents--S--, --O-- or ##STR8## wherein R³ has the abovementioned meaning, andif two substituents R³ occur, these can be identical or different,

R⁴ and R⁵ either represent hydrogen, or together represent the remainingmembers of a fused-on benzene ring, and

R⁶ represents C₁ -C₄ -(di)alkylamino, C₆ -C₁₀ -(di)arylamino,piperazino, pyrrolidino, C₁ -C₄ -alkylmercapto or C₆ -C₁₀ -arylmercapto,

B represents a radical of the formula ##STR9## wherein R representshydrogen, a C₁ -C₄ -alkyl radical which is optionally substituted byhydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carbonyl, aminocarbonyl or C₁-C₄ -alkoxycarbonyl, or represents a phenyl, benzyl or phenylethylradical which in each case is optionally substituted by halogen, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy and

R¹ represents a C₁ -C₄ -alkyl radical which is optionally substituted byhydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl, aminocarbonyl or C₁-C₄ -alkoxycarbonyl, or represents a benzyl or phenylethyl radical whichin each case is optionally substituted by halogen, C₁ -C₄ -alkyl or C₁-C₄ -alkoxy, and

R² represents hydrogen, a C₁ -C₈ -alkyl radical which is optionallysubstituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl,aminocarbonyl or C₁ -C₄ -alkoxycarbonyl or represents a benzyl orphenylethyl radical which in each case is optionally substituted byhalogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

In the definition of R³, R⁶ and X C₁ -C₄ -(di)-alkylamino means C₁ -C₄-alkylamino and C₁ -C₄ -dialkylamino. In the definition of R⁶ C₆ -C₁₀-(di)-arylamino means C₆ -C₁₀ -arylamino and C₆ -C₁₀ -diarylamino.

The new triazatrimethine dyestuffs of the formula (I) can be prepared ina known manner by reaction of colour bases of the formula (II) ##STR10##wherein

B and Z have the abovementioned meanings, with an alkylating agent fromthe class comprising alkyl halides, Michael acceptors or epoxides, suchas are also mentioned, for example, in DE-A 2 811 258 on page 34.

In the case where the substituent B in formula (II) does not cause muchsteric hindrance, quaternisation in the 4-position of the thiadiazolering can also occur to a certain percentage, which is usually less than10%, during the reaction with the quaternising agent.

The colour bases of the formula (II) are likewise new, and the presentinvention relates to them. The colour bases of the formula (II) arelikewise dyestuffs, and the invention furthermore relates to the usethereof for dyeing fibres and fabrics of materials which can be dyedwith non-ionic dyestuffs, for example polyesters, and for dyeingplastics, especially for bulk dyeing of plastics such as, for example,polystyrene, polycarbonate, polyamide or acrylonitrile/butadiene/styrenecopolymers.

The colour bases of the formula (II) can be prepared in a manner whichis known per se, for example by the process described in DE-A 1 069 563,by diazotisation of heterocyclic amines and coupling to quaternary saltsof the same or different heterocyclic amines. The diazotisation iscarried out with alkali metal nitrites in aqueous mineral acid solutionor in an aqueous solution of an organic acid. The diazonium saltsolution thus obtained is combined with the solution of the couplingcomponent, and the product is isolated, for example by filtration, ifappropriate after buffering.

Alternatively, the new dyestuffs of the formula (II) can be prepared bya new process, to which the present invention likewise relates. The newprocess for the preparation of dyestuffs of the formula (II) ischaracterised in that a compound of the formula (IV) ##STR11## wherein Bhas the abovementioned meaning,

and a compound of the formula (V)

    H--Z.sup.1                                                 (V)

wherein

Z¹ represents a radical of the formula ##STR12## wherein R³ and An.sup.⊖have the abovementioned meaning and

X¹ represents the remaining members of a quaternised five-memberedoptionally substituted and optionally fused, unsaturated heterocyclicring which contains 1 to 3 hereto atoms selected from the groupconsisting of oxygen, sulphur and nitrogen, and preferably representsthe remaining members of a quaternised thiazole, isothiazole,benzothiazole, 1,2,4-triazole, 1,3,4-thiadiazole, oxazole, benzoxazole,imidazole, benzimidazole, pyrazole or benzopyrazole ring, which is ineach case optionally mono- or dlsubstituted by identical or different C₁-C₈ -alkyl, which is optionally substituted by hydroxyl, halogen, cyano,C₁ -C₄ -alkoxy, carboxyl, C₁ -C₄ -(di)alkylamino, C₁ -C₄ -alkoxycarbonylor C₁ -C₄ -alkylsulphonyl, or represents C₂ -C₄ -alkenyl, or representsphenyl-C₁ -C₄ -alkyl, which is optionally substituted by halogen, cyano,C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

are reacted in an aqueous medium with a substance which donates nitrousacid, in the presence of CO₂ under a pressure of 5 to 100 bar and at atemperature of 0° to 125° C. The reaction has in general ended after 10minutes to 24 hours.

The process according to the invention is preferably carried out at atemperature from 0° to 100° C. particularly preferably from 0° to 70°C., and in particular from 30° to 40° C.

Water, if appropriate mixed with organic solvents which are completelyor partly miscible with water, is suitable as the reaction medium.

Possible suitable solvents are methanol, ethanol, propanol, isopropanol,isoamyl alcohol, ethylene glycol, methylglycol, ethylglycol,butylglycol, ethylene glycol dimethyl ether, ethylene glycol diethylether, diethylene glycol dimethyl ether, glycol diacetate, methylglycolacetate, ethylglycol acetate, butylglycol acetate, propylene glycol,propylene glycol monomethyl ether, propylene glycol monoethyl ether,propylene glycol dimethyl ether, propylene glycol diethyl ether,propylene glycol acetate, triacetin, acetonitrile, tetrahydrofuran,dioxane, dimethylformamide and N-methyl-pyrrolidone.

It is preferable to use water or a mixture of water and methanol whichhas a ratio of water to methanol of preferably 1:0.2 to 1:10,particularly preferably 1:1 to 1:5 and in particular 1:2.

No reaction with CO₂ takes place under normal pressure. The reaction ispreferably carried out under a pressure of 25 to 65 bar.

Inorganic and organic nitrites arc particularly suitable substancesdonating nitrous acid.

Preferred inorganic nitrites are the nitrous acid salts of elements ofthe first, second and third main groups of the periodic system and ofthe transition metals such as for example lithium nitrite, sodiumnitrite, potassium nitrite, magnesium nitrite, calcium nitrite,aluminium nitrite, iron nitrite or copper nitrite.

Preferred organic nitrites are nitrous acid esters of the formula

    E--O--N═O,

wherein

E represents a C₁ -C₁₀ -alkyl radical which is optionally substituted byOH, O-alkyl, O-acetyl or ONO.

The following organic nitrites may be mentioned as examples:

methyl nitrite, ethyl nitrite, n-propyl nitrite, i-propyl nitrite,n-butyl nitrite, i-butyl nitrite, s-butyl nitrite, n-pentyl nitrite,i-pentyl nitrite, all of the isomers of hexyl, heptyl and octylnitrites, 2-methoxyethyl nitrite, 2-ethoxyethyl nitrite, 2-propoxyethylnitrite, 2-butoxyethyl nitrite and 1-methoxyprop-2-yl nitrite, as wellas nitrous acid mono- and diesters of 1,2-ethanediol, 1,2-propanediol,1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol,2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,2,2-diethyl-1,3-propanediol, 1-propyl-2-ethyl-1,3-propanediol,1-propyl-2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol,diethylene glycol, di-1,2-propyleneglycol and triethylene glycol andfurther of the methyl, ethyl, propyl and butyl half-ethers of diethyleneglycol, di-1,2-propylene glycol and triethylene glycol as well asnitrous acid esters of pentaerythritol and the alkyl ethers derivedtherefrom.

The preparation of triazatrimethine dyestuffs has hitherto been carriedout by diazotisation of the aromatic or heterocyclic amines in mineralacid solution, addition of the diazonium salt solution to the solutionof the coupling component and coupling by addition of acid-bindingagents (compare, for example, DE-A 1 069 563).

In all cases, an inorganic or organic acid was hitherto employed for thediazotisation and had to be neutralised during the subsequent coupling.Inorganic salts are formed here. These inorganic salts enter the wastewater during isolation of the dyestuff and represent pollution. Whenmixed with the dyestuff prepared, inorganic salts often influence thesolubility in an adverse manner. To prepare stable dyestuff solutions,these salts must be removed by expensive processes, for example pressurepermeation or reverse osmosis. All these disadvantages can be avoided bythe new preparation process according to the invention.

The dyestuffs of the formula (I) according to the invention areparticularly suitable for dyeing and printing naturally occurring andsynthetic materials, in particular fibres of polyacrylonitrile,acid-modified polyesters and polyamides.

Dyeing can be carried out from a weakly acid liquor, the goodsexpediently being introduced into the dyebath at 40° to 60° C. anddyeing then being carried out at the boiling point. Dyeing can also becarried out under pressure at temperatures above 100° C. The dyestuffsfurthermore can be added to spinning solutions for production of fibrescontaining polyacrylonitrile, or can also be applied to thenon-stretched fibre.

Dyeings of the dyestuffs of the formula (I) according to the inventionon materials of polyacrylonitrile or acid-modified polyester fibres orpolyamide fibres are distinguished by very good fastness to light, wetprocessing, rubbing and sublimation and by a high affinity for thefibre.

Examples of compounds of the formula (IV) are:

2,5-diamino-1,3,4-thiadiazole,2-amino-5-(di)methylamino-1,3,4-thiadiazole,2-amino-5-(di)ethylamino-1,3,4-thiadiazole,2-amino-5-(di)-n-propylamino-1,3,4-thiadiazole,2-amino-5-(di)-i-propylamino-1,3,4-thiadiazole,2-amino-5-(di)butylamino-1,3,4-thiadiazole,2-amino-5-(di)phenylamino-1,3,4-thiadiazole,2-amino-5-phenylmethylamino-1,3,4-thiadiazole,2-amino-5-(di)benzylamino-1,3,4-thiadiazole,2-amino-5-benzylmethylamino-1,3,4-thiadiazole,2-amino-5-phenethylmethylamino-1,3,4-thiadiazole,2-amino-5-morpholino-1,3,4-thiadiazole,2-amino-5-piperidino-1,3,4-thiadiazole,2-amino-5-pyrrolidino-1,3,4-thiadiazole,2-amino-5-(di)cyclohexylamino-1,3,4-thiadiazole,2-amino-5-cyclohexylmethylamino-1,3,4-thiadiazole,2-amino-5-hydroxyethylmethylamino-1,3,4-thiadiazole,2-amino-5-(di)hydroxyethylamino-1,3,4-thiadiazole,2-amino-5-(di)hydroxypropylamino-1,3,4-thiadiazole,2-amino-5-cyanoethylmethylamino-1,3,4-thiadiazole and2-amino-5-biscyanoethylamino-1,3,4-thiadiazole.

Examples of quaternary salts of heterocyclic amines of the formula (V)which can be employed are:

2-amino-3-methylbenzothiazolium, 2-amino-3-ethylbenzothiazolium,2-amino-3-methyl-6-methylbenzothiazolium,2-amino-3-methyl-6-methoxybenzothiazolium,2-amino-3-methyl-6-nitrobenzothiazolium,2-amino-3-methyl-6-ethoxybenzothiazolium,2-amino-3-methyl-1,3-thiazolium,2-amino-3-methyl-5-methyl-1,3-thiazolium,2-amino-3-methyl-5-ethyl-1,3-thiazolium,2-amino-3-methyl-5-t-butyl-1,3-thiazolium,2-amino-3-methyl-5-phenyl-1,3-thiazolium,2-amino-3-methyl-4,5-dimethyl-1,3-thiazolium,2-amino-3-methyl-4,5-diphenyl-1,3-thiazolium,3-amino-1,4-dimethyl-1,2,4-triazolium,3-amino-1,4-diethyl-1,2,4-triazolium,3-amino-1,4-dimethyl-5-ethyl-1,2,4-triazolium,3-amino-1,4-dimethyl-5-cyanoethyl-1,2,4-triazolium,3-amino-1,4-dimethyl-5-butyl-1,2,4-triazolium,3-amino-1,4-dimethyl-5-phenyl-1,2,4-triazolium,3-amino-1,4-dimethyl-5-p-tolyl-1,2,4-triazolium,2-amino-5-(di)methylamino-1,3,4-thiadiazolium,2-amino-5-(di)ethylamino-1,3,4-thiadiazolium,2-amino-5-(di)-n-propylamino-1,3,4-thiadiazolium,2-amino-5-(di)-i-propylamino-1,3,4-thiadiazolium,2-amino-5-(di)-n-butylamino-1,3,4-thiadiazolium,2-amino-5-(di)-phenylamino-1,3,4-thiadiazolium,2-amino-5-phenylmethylamino-1,3,4-thiadiazolium,2-amino-5-benzylmethylamino-1,3,4-thiadiazolium,2-amino-5-phenethylmethylamino-1,3,4-thiadiazolium,2-amino-5-morpholino-1,3,4-thiadiazolium,2-amino-5-piperidino-1,3,4-thiadiazolium,2-amino-5-pyrrolidino-1,3,4-thiadiazolium,2-amino-5-(di)cyclohexylamino-1,3,4-thiadiazolium,2-amino-5-cyclohexylmethylamino-1,3,4-thiadiazolium,2-amino-5-(di)hydroxyethylmethylamino-1,3,4-thiadiazolium and2-amino-5-cyanoethylmethylamino-1,3,4-thiadiazolium salts.

The quaternary salts of the formula (V) are obtainable, for example, byreaction of compounds of the formula (IV) with a quaternising agent,such as, for example, methyl iodide, ethyl iodide, propyl iodide, butyliodide, dimethyl sulphate, ethylene oxide, propylene oxide,acrylonitrile, acrylamide, acrylic acid and its esters,α-halogenocarboxylic acids and their esters or epichlorohydrin.

The following examples are intended to illustrate the present invention.

EXAMPLE 1

20 g of 2-amino-5-diisopropylamino-1,3,4-thiadiazole, 27.6 g of2-amino-3-methyl-1,3-benzothiazolium methosulphate, 12 g of isoamylnitrite, 40 ml of water and 80 ml of methanol are combined in anautoclave, and the mixture is placed under a CO₂ pressure of 50 bar andheated to 40° C. It is stirred at this temperature under a constantpressure for 3 hours. The autoclave is then let down, the methanol isdistilled off and the colour base of the formula ##STR13## is dischargedonto water and filtered off with suction. After drying, the yield is28.5 g, melting point: 195°-198° C.

Methylation with dimethyl sulphate gives a cationic dyestuff which dyespolyacrylonitrile in a light-fast red shade and corresponds to theformula ##STR14## Similarly useful dyestuffs are obtained if, instead of2-amino-3-methyl- 1,3-benzothiazolium methosulphate, the methylatedquaternary salts of 3-aminotriazole, of 2-aminothiazole or of2-amino-diisopropylamino- 1,3,4-thiadiazole are employed for thesynthesis of the colour base.

The colour bases of the formula (II) listed in Table 1 which, afterquaternisation, lead to the corresponding dyestuffs of the formula (I),which have the absorption wavelengths stated in Table 1, can be preparedanalogously to Example 1.

    TABLE 1            Example      ##STR15##      Quaternising agent      ##STR16##      An.sup.⊖ λ.sub.max      [nm]                                          2      ##STR17##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     490      3     ##STR18##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     492      4     ##STR19##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     492      5     ##STR20##      Acrylonitrile R.sup.2 = CH.sub.2 CH.sub.2 CN Cl.sup.⊖ 465  6      ##STR21##      Benzyl chloride      ##STR22##      Cl.sup.⊖ 498      7     ##STR23##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     505      8     ##STR24##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     492      9     ##STR25##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     498      10     ##STR26##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     500      11     ##STR27##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     496      12     ##STR28##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     494      13     ##STR29##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     496      14     ##STR30##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     496      15     ##STR31##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     490      16     ##STR32##      Dimethyl sulphate R.sup.2 = CH.sub.3 CH.sub.3 SO.sub.4.sup.⊖     488

What is claimed is:
 1. A triazatrimethine dyestuff of the formula (I)##STR33## ##STR34## wherein Z represents a radical of the formula##STR35## wherein R³ represents hydrogen or an alkyl, alkenyl or aralkylradical andX represents the remaining members of a five-membered,optionally substituted and optionally fused partly unsaturatedheterocyclic ring which contains one to three hereto atoms selected fromthe group consisting of oxygen, sulphur and nitrogen, B representsalkylmercapto, arylmercapto or a radical of the formula ##STR36##wherein R denotes hydrogen or an alkyl, alkenyl, acyl, cycloalkyl, aryl,aralkyl, amino, alkylamino, dialkylamino, arylamino, aralkylamino orheterocyclic radical and R¹ denotes hydrogen or an alkyl, alkenyl oraralkyl radical, or R and R¹ together with the nitrogen atom to whichthey are attached form a heterocyclic ring, R₂ represents hydrogen or analkyl, alkenyl, alkinyl or aralkyl radical and An.sup.(-) represents ananion,and wherein the cyclic and acyclic radicals can contain non-ionicsubstituents and/or a carboxyl group.
 2. Triazatrimethine dyestuff ofclaim 1, whereinZ represents a radical of the formula ##STR37## whereinR³ represents hydrogen, or represents C₁ -C₈ -alkyl which is optionallysubstituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl, C₁-C₄ -alkylamino, C₁ -C₄ -dialkylamino, C₁ -C₄ -alkoxycarbonyl or C₁ -C₄-alkylsulphonyl, or represents C₂ -C₄ -alkenyl, or represents phenyl-C₁-C₂ -alkyl, which is optionally substituted by halogen, cyano, C₁ -C₄-alkyl or C₁ -C₄ -alkoxy and X represents the remaining members of athiazoline, isothiazoline, benzothiazoline, 1,2,4-triazoline,1,3,4-thiadiazoline, oxazoline, benzoxazoline, imidazoline,benzimidazoline, pyrazoline or benzopyrazoline ring, which is in eachcase optionally mono- or disubstituted by identical or different C₁ -C₈-alkyl, which is optionally substituted by hydroxyl, halogen, cyano, C₁-C₄ -alkoxy, carboxyl, C₁ -C₄ -alkylamino, C₁ -C₄ -dialkylamino, C₁ -C₄-alkoxycarbonyl or C₁ -C₄ -alkylsulphonyl, or represents C₂ -C₄-alkenyl, or represents phenyl-C₁ -C₂ -alkyl, which is optionallysubstituted by halogen, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, Brepresents a radical of the formula ##STR38## wherein R representshydrogen, or represents a C₁ -C₈ -alkyl radical which is optionallysubstituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl,aminocarbonyl or C₁ -C₄ -alkoxycarbonyl, or represents a C₂ -C₄ -alkenylradical, a cyclohexyl radical which is optionally substituted by C₁ -C₄-alkyl, or represents a phenyl, benzyl or phenylethyl radical which ineach case is optionally substituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy, or represents a C₁ -C₄ -alkyloxycarbonyl, mono- or di-C₁ -C₄-alkylaminocarbonyl, aminocarbonyl, mono- or di-C₁ -C₄-alkylaminosulphonyl, amino, C₁ -C₄ -alkylamino or C₁ -C₄ -dialkylaminoradical, or represents a phenylamino or benzylamino radical which ineach case is optionally substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxyand R¹ represents hydrogen, a C₁ -C₈ -alkyl radical which is optionallysubstituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl,aminocarbonyl or C₁ -C₄ -alkoxycarbonyl, or represents a C₂ -C₄ -alkenylradical or represents a phenyl, benzyl or phenylethyl radical which ineach case is optionally substituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄-alkoxy, and R² represents hydrogen, a C₁ -C₈ -alkyl radical which isoptionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy,carboxyl, aminocarbonyl or C₁ -C₄ -alkoxycarbonyl, or represents a C₂-C₄ -alkenyl radical or represents a benzyl or phenylethyl radical whichin each case is optionally substituted by halogen, C₁ -C₄ -alkyl or C₁-C₄ -alkoxy.
 3. Dyestuff of claim 1, whereinZ represents a radical ofthe formula ##STR39## wherein Y represents --S--, --O-- or ##STR40##wherein R³ has the abovementioned meaning, and if two substituents R³occur, these can be identical or different, R⁴ and R⁵ either representhydrogen, or together represent the remaining members of a fused-onbenzene ring, and R⁶ represents C₁ -C₄ -alkylamino, C₆ -C₁₀-dialkylamino, C₆ -C₁₀ -arylamino, C₆ -C₁₀ -diarylamino, piperazino,pyrrolidino, C₁ -C₄ -alkylmercapto or C₆ -C₁₀ -arylmercapto, Brepresents a radical of the formula ##STR41## wherein R representshydrogen, a C₁ -C₄ -alkyl radical which is optionally substituted byhydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carbonyl, aminocarbonyl or C₁-C₄ -alkoxycarbonyl, or represents a phenyl, benzyl or phenylethylradical which in each case is optionally substituted by halogen, C₁ -C₄-alkyl C₁ -C₄ -alkoxy and R¹ represents a C₁ -C₄ -alkyl radical which isoptionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy,carboxyl, aminocarbonyl or C₁ -C₄ -alkoxycarbonyl, or represents abenzyl or phenylethyl radical which in each case is optionallysubstituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, and R²represents hydrogen, a C₁ -C₈ -alkyl radical which is optionallysubstituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl,aminocarbonyl or C₁ -C₄ -alkoxycarbonyl or represents a benzyl orphenylethyl radical which in each case is optionally substituted byhalogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.
 4. Dyestuff of the formula##STR42## wherein Z represents a radical of the formula ##STR43##wherein R³ represents hydrogen or an alkyl, alkenyl or aralkyl radicalandX represents the remaining members of a five-membered, optionallysubstituted and optionally fused partly unsaturated heterocyclic ringwhich contains one to three hereto atoms selected from the groupconsisting of oxygen, sulphur and nitrogen, B represents alkylmercapto,arylmercapto or a radical of the formula ##STR44## wherein R denoteshydrogen or an alkyl, alkenyl, acyl, cycloalkyl, aryl, aralkyl, amino,alkylamino, dialkylamino, arylamino, aralkylamino or heterocyclicradical and R¹ denotes hydrogen or an alkyl, alkenyl or aralkyl radical,or R and R¹ together with the nitrogen atom to which they are attachedform a heterocyclic ring, R² represents hydrogen or an alkyl, alkenyl,alkinyl or aralkyl radical and An.sup.(-) represents an anion. 5.Dyestuff of claim 4, whereinZ represents a radical of the formula##STR45## wherein R³ represents hydrogen, C₁ -C₈ -alkyl which isoptionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy,carboxyl, C₁ -C₄ -alkylamino, C₁ -C₄ -dialkylamino, C₁ -C₄-alkoxycarbonyl or C₁ -C₄ -alkylsulphonyl, or represents C₂ -C₄-alkenyl, or represents phenyl-C₁ -C₂ -alkyl, which is optionallysubstituted by halogen, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy and Xrepresents the remaining members of a thiazoline, isothiazoline,benzothiazoline, 1,2,4-triazoline, 1,3,4-thiadiazoline, oxazoline,benzoxazoline, imidazoline, benzimidazoline, pyrazoline orbenzopyrazoline ring, which is in each case optionally mono- ordisubstituted by identical or different C₁ -C₈ -alkyl, which isoptionally substituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy,carboxyl, C₁ -C₄ -alkylamino, C₁ -C₄ -dialkylamino, C₁ -C₄-alkoxycarbonyl or C₁ -C₄ -alkylsulphonyl, or represents C₂ -C₄-alkenyl, or represents phenyl-C₁ -C₂ -alkyl, which is optionallysubstituted by halogen, cyano, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, Brepresents a radical of the formula ##STR46## wherein R representshydrogen, a C₁ -C₈ -alkyl radical which is optionally substituted byhydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl, aminocarbonyl or C₁-C₄ -alkoxycarbonyl, or represents a C₂ -C₄ -alkenyl radical, acyclohexyl radical which is optionally substituted by C₁ -C₄ -alkyl, orrepresents a phenyl, benzyl or phenylethyl radical which in each case isoptionally substituted by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, orrepresents a C₁ -C₄ -alkyloxycarbonyl, mono- or di-C₁ -C₄-alkylaminocarbonyl, aminocarbonyl, mono- or di-C₁ -C₄-alkylaminosulphonyl, amino, C₁ -C₄ -alkylamino or di-(C₁ -C₄-alkyl)-amino radical, or a phenylamino or benzylamino radical which isoptionally substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy and R¹represents hydrogen, a C₁ -C₈ -alkyl radical which is optionallysubstituted by hydroxyl, halogen, cyano, C₁ -C₄ -alkoxy, carboxyl,aminocarbonyl or C₁ -C₄ -alkoxycarbonyl, or represents a C₂ 14 C₄-alkenyl radical or represents a phenyl, benzyl, or phenylethyl radicalwhich in each case is optionally substituted by halogen, C₁ -C₄ -alkylor C₁ -C₄ -alkoxy, and R² represents hydrogen, a C₁ -C₈ -alkyl radicalwhich is optionally substituted by hydroxyl, halogen, cyano, C₁ -C₄-alkoxy, carboxyl, aminocarbonyl or C₁ -C₄ -alkoxycarbonyl, orrepresents a C₂ -C₄ -alkenyl radical or represents a benzyl orphenylethyl radical which in each case is optionally substituted byhalogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.
 6. A process for dyeing andprinting naturally occurring and synthetic matrials by applying theretoat least one dyestuff of the formula (I) of claim
 1. 7. A process fordyeing and printing naturally occurring and synthetic materials byapplying thereto at least one dyestuff of the formula (II) of claim 4 isemployed.
 8. A process for bulk dyeing of plastics by applying theretoat least one dyestuff of the formula (II) of claim
 4. 9. A processaccording to claim 6 wherein the naturally occuring and syntheticmaterials are fibres of polyacrylonitrile, acid-modified polyesters andpolyamides.
 10. A process according to claim 7 wherein the naturallyoccuring and synthetic materials are fibres and fabrics of materialswhich can be dyed with nonionic dyestuffs.
 11. A dyestuff mixture whichcontains at least two dyestuffs of the formula (I) of claim
 1. 12. Adyestuff mixture which contains at least two dyestuffs of the formula(II) of claim 4.